Hemisynthesis of new triterpene derivatives using oxidation by CrO3 and NaIO4-(RuCl3, 3H2O)

Article abstract of DOI:10.1080/00397910701226756

Oxidation of triterpenes resulting from E. resinifera, E. officinarum, and their derivatives, using chromic anhydride (CrO3) and the system NaIO4-(RuCl3,3H2O), gives carbonyl triterpenic compounds with high chemioselectivity. Copyright Taylor & Francis Gr

Full text of DOI:10.1080/00397910701226756

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Hemisynthesis of New Triterpene Derivatives
using Oxidation by CrO3 and NaIO4‐(RuCl3,
3H2O)
N. Mazoir a , A. Auhmani a , M. Daoubi a , I. G. Collado b & A. Benharref a
a Chemistry Laboratory of Natural Substances , University Cadi Ayyad,
Faculty of Sciences Semlalia , Marrakech, Morocco
b Department of Organic Chemistry, Faculty of Sciences , University of
Cádiz , Cádiz, Spain
Published online: 12 Apr 2007.
To cite this article: N. Mazoir , A. Auhmani , M. Daoubi , I. G. Collado & A. Benharref (2007) Hemisynthesis
of New Triterpene Derivatives using Oxidation by CrO3 and NaIO4‐(RuCl3, 3H2O), Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:8, 1289-1299, DOI:
10.1080/00397910701226756
To link to this article: http://dx.doi.org/10.1080/00397910701226756
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Synthetic Communicationsw, 37: 1289–1299, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701226756
Hemisynthesis of New Triterpene
Derivatives using Oxidation by CrO3
and NaIO4-(RuCl3, 3H2O)
N. Mazoir, A. Auhmani, and M. Daoubi
Chemistry Laboratory of Natural Substances, University Cadi Ayyad,
Faculty of Sciences Semlalia, Marrakech, Morocco
I. G. Collado
Department of Organic Chemistry, Faculty of Sciences, University of
´ ´
Cadiz, Cadiz, Spain
A. Benharref
Chemistry Laboratory of Natural Substances, University Cadi Ayyad,
Faculty of Sciences Semlalia, Marrakech, Morocco
Abstract: Oxidation of triterpenes resulting from E. resinifera, E. officinarum, and
their derivatives, using chromic anhydride (CrO3) and the system NaIO4-
(RuCl3,3H2O), gives carbonyl triterpenic compounds with high chemioselectivity.
Keywords: Euphorbia officinarum, Euphorbia resinifera, hemisynthesis, latex,
oxidation
The isolated triterpenes of Euphorbia resinifera[1] and Euphorbia offici-
narum[1–3] were subjected to hemisynthesis in order to prepare new
carbonyl triterpenic compounds with good yield. The oxygenated triterpenic
compounds exhibit good pharmacological activities. Some polyoxygenated
tritepenics were proved to have the cytotoxicity against hepatoma cells in
vitro.[4] Some others, isolated from Ganoderma lucidum, are effective as
Received in the U.K. April 27, 2006
Address correspondence to A. Benharref, Chemistry Laboratory of Natural
Substances, University Cadi Ayyad, Faculty of Sciences Semlalia, P.O. Box 2390,
Marrakech 40000, Morocco. E-mail: benharref@ucam.ac.ma
1289

1290
N. Mazoir et al.
cytotoxic,[5] antiviral,[6] and anti-inflammatory agents.[7,8] They have been
shown to inhibit farnesyl-protein transferase[9] and also cucurbitacin picfeltar-
raegenin I.[10]
To prepare a similar compound, we have used the oxidation of isolated
triterpenes resulting from Moroccan cactoid euphorbium and their derivatives
with chromic anhydride[11] and catalytic oxidation using ruthenium trichlo-
ride[12] in the presence of sodium periodate.
Thus, we were interested in the oxygenated triterpenic compounds in
positions 3, 7, 11, and 24 because the access to triterpenic ketones in
positions 3, 7, and 11 can be carried out by oxidation with chromic
anhydride. On the other hand, the synthesis of carbonyl triterpenic derivatives
in position 24 can be carried out using catalytic oxidation with the system
NaIO4-(RuCl3, 3H2O), like an organic oxidant.
Oxidation with the system NaIO4-(RuCl3,3H2O) of eupho lanosta-8,24-
dien-3b-ol (1), a major triterpene isolated from Euphorbia resinifera latex,
followed by esterification and then acetylation reaction, led to the title
compound (3S,5S,10S,13S,14S,17S)3b-acetyl-25,26,27-trisnorlanost-8-en-
24-oate (2) in 75% yield (Scheme 1).
The compound 2 was characterized more precisely in 1H NMR by a doublet
(of doublet) (J1 ¼ 12 Hz, J2 ¼ 4 Hz) at 4.44 ppm, due to the resonance of H-3.
The methyl of ester group was observed as a singulet at 3.58 ppm. 13C NMR
spectrum exhibits 30 signals. Those observed at 81.07, 171.18, and
174.87 ppm were assigned respectively to C3 and CO of acetyl group and C24.
The relative stereochemistry of the title compound 2 was assigned to a
known chiral center and confirmed by its single X-ray structure (Fig. 1).[12]
Treatment of 8a,9a-epoxy-4a,14a-dimethyl-5a-cholestan-3b-ol (3), a
triterpene derivative from Euphorbia officinarum latex, with 3 equiv. of
chromic anhydride yielded compound 4 in 85% yield (Scheme 2).
Structure elucidation of carbonyl compound 4 was based on spectral data
1
including H NMR, 13C NMR, and mass spectrometry. 13C NMR spectrum
exhibits a signal at 212.40 ppm due to the resonance of C3.
The stereochemistry has been confirmed by single-crystal X-ray diffrac-
tion (Fig. 2).[13]
Acylation[14] of 4a-14a-dimethyl-5a-cholest-8-en-3b-ol 5, a major triter-
pene isolated from Euphorbia officinarum latex, followed by oxidation with 3
equiv. of CrO3 during 12 h, gave two functionalized triterpenes 6 and 7
Scheme 1.

Triterpene Derivatives
1291
Figure 1. ORTEP drawing of 2.
1
(Scheme 3). H NMR spectrum of minor product 6 showed more precisely a
multiplet at 4.39 ppm assigned to the H-3 proton. In 13C NMR, a carbonyl
group at C7 would have resonated at 197.50 ppm. The structure of the
major product 7 was elucidated from 1H NMR, 13C NMR, and mass spectro-
scopic data. Thus, its molecular formula C31H48O4 was determined from
molecular ion m/z ¼ 584 in its mass spectrum. 13C NMR indicated the
presence of 31 carbons, which include two carbonyl groups at 201.02 and
202.50 ppm, due to the resonance of C7 and C11 respectively.
The stereochemistry of compound 7 has been confirmed by single-crystal
X-ray diffraction (Fig. 2).[15]
Scheme 2.

1292
N. Mazoir et al.
Figure 2. ORTEP drawing of 4.
Treatment with tosyle chloride followed by an oxidation condition similar
to that before gave triterpenic compounds 8 and 9 (Scheme. 3).[16]
13C NMR spectrum revealed that 8 has one carbonyl group at C7, whereas
compound 9 has two carbonyl groups at C7 and C11. The structure and
relative stereochemistry of the title compound 9 were established and
confirmed by single-crystal X-ray diffraction (Fig. 3).[17]
Tosylation of 4a-14a-dimethyl-5a-ergost-8-en-3b-ol 10, a major triter-
pene isolated from Euphorbia officinarum latex, followed by catalytic
oxidation similar to that before, gave compound 11 with a good yield
(75%) (Scheme 4).
Structure of 11 was elucidated from 1H and 13C NMR. Thus the multiplet
at 4.09 ppm was assigned to H-3 proton. In 13C NMR spectrum, carbonyl
group at C24 was observed at 215.50 ppm.
Oxidation of compound 11 by 3 equiv. with chromic anhydride leads to
preparation of two carbonyl compounds, 12 and 13 (Scheme 5).
13C NMR spectrum of 12 showed more precisely two signals at 198.50
and 215.45 ppm, assigned respectively to C7 and C24, whereas the carbonyl
groups at C7, C11, and C24 resonated respectively at 200.68, 202.35, and
214.54 ppm for compound 13.
Scheme 3.

Triterpene Derivatives
1293
Figure 3. ORTEP drawing of 9.
The structure of compound 13 was performed on the basis of X-ray
single-crystallography analysis (Fig. 4).
In summary, we have synthesized the novel carbonyl compounds 2, 4, 6,
7, 8, 9, 11, 12, and 13 with a good yield via an oxidative route.
The ruthenium-catalyzed oxidation was proved to be effective and
chemeoselective.
EXPERIMENTAL
1
The H and 13C NMR spectrum were recorded on AMX2 Bru¨ker 500-Hz
(1H 500 MHz, 13C 125 MHz) using TMS as an internal standard and CDCl3
as the solvent. The melting points were measured in capillaries on a Buchi
510 apparatus. The chemical shifts are given in ppm. The multiplicity of
Scheme 4.

1294
N. Mazoir et al.
Scheme 5.
the signals observed is indicated by the letters: singlet (s), doublet (d), triplet
(t), quadruplet (q), doublet and doublet (dd), and triplet dedoublet (td). Mass
spectra were obtained with an Autospect Instrument 70-ev spectrometer.
Column chromatography was carried out on silica gel (Merk Art. 15111,
7741); eluent: hexane–ethyl acetate. The X-ray diffraction measurements
were carried out on an automated diffractometer, Nonius CCD, with mono-
chromated Mo Ka (l ¼ 0.71073) radiation.
General Procedure of Oxidation using NaIO4-(RuCl3, 3H2O)
The sodium periodate was prepared in situ with a equimolar quantity of soda
NaOH (0.5 g; 12.50 mmol) and periodic acid H5IO6 (2.85 g; 12.50 mmol).
The mixture was stirred at 08C. After 15 min, 5 ml of CCl4, 5 ml of
H3CCN, and 32.70 mg (0.12 mmol) of ruthenium trichloride were added.
The mixture was stirred during 15 mn, then 1.33 g (3.12 mmol) of 1 was
added. The reaction was left under agitation at 258C for 30 h, then 20 ml of
distilled water was added, and the reaction mixture was extracted with
40 ml of dichloromethane, dried over sodium sulphate, and reduced in
Figure 4. ORTEP drawing of 13.

Triterpene Derivatives
1295
vacuum to afford a black solid. The latter was filtered on a silica-gel column to
eliminate RuO4. The organic layer is recovered and evaporated under reduced
pressure. The residue was purified on a silica-gel column using hexane/
EtOAc (90:10) as an eluent.
General Procedure of Oxidation with CrO3
To a solution of 1.00 g (2.34 mmol) of 3 in 20 ml of acetone, 0.70 g
(7.04 mmol) of chromic anhydride was added. The mixture was maintained
at 08C for 3 h (12 h for allylic oxidation), washed with 20 ml of cold water,
and extracted with ethyl acetate. The organic layer was dried over Na2SO4
and concentrated under reduced pressure. The residue was purified on a
silica-gel column using hexane/EtOAc (95:5) as an eluent.
Data
(3S,5S,10S,13S,14S,17S)3b-Acetyl-25,26,27-trisnorlanost-8-en-24-oate (2):
1
mp ¼ 176–1778C (methanol), yield: 75%. H NMR (500 MHz, CDCl3) d
(ppm): 4.43 (H-3, dd, J1 ¼ 12 Hz, J2 ¼ 4 Hz); 3.64 (COOCH3), 1.98
(OCOCH3), 0.75 (H-18), 1.00 (H-19, s), 0.95 (H-21, d, J ¼ 6.2 Hz, 0.96 (H-
25, s), 0.97 (H-26, s), 0.90 (H-27, s). 13C NMR (125 MHz, CDCl3) d (ppm):
35.28 (C-1), 35.84 (C-2), 81.32 (C-3), 51.8 (C-4), 51.43 (C-5), 31.10 (C-6),
30.70 (C-7), 133.9 (C-8), 134.3 (C-9), 49.8 (C-10), 28.43 (C-11), 28.37
(C-12), 44.48 (C-13), 38.24 (C-14), 27.89 (C-15), 24.80 (C-16), 50.39 (C-17),
15.85 (C-18), 20.57 (C-19), 31.43 (C-20), 18.99 (C-21), 31.11 (C-22), 37.52
(C-23), 175.09 (C-24), 24.62 (C-25), 21.88 (C-26), 16.99 (C-27), 20.57
(COOCH3), 21.69 (OCOCH3).
8a,9a-Epoxy-4a,14a-dimethyl-5a,cholestan-3-one (4): mp ¼ 128–1298C
1
(hexane), yield: 85%. H NMR (500 MHz, CDCl3) d (ppm): 0.73 (H-18, s),
0.83 (H-19, s), 0.82 (H-21, d, J ¼ 6 Hz), 0.77 (H-26, d, J ¼ 2 Hz), 0.80
(H-27, J ¼ 2 Hz), 1.25 (H-28, s), 0.87 (H-29, d, J ¼ 6.2 Hz). 13C NMR
(125 MHz, CDCl3) d (ppm): 36.3 (C-1), 36.4 (C-2), 212.4 (C-3), 49.2 (C-4)
45.4 (C-5), 22.7 (C-6), 22.0 (C-7), 69.6 (C-8), 68.3 (C-9), 36.4 (C-10), 19.4
(C-11), 26.5 (C-12), 43.9 (C-13), 43.3 (C-14), 30.9 (C-15), 29.3 (C-16),
48.6 (C-17), 15.9 (C-18), 15.5 (C-19), 36.4 (C-20), 19.6 (C-21), 36.2
(C-22), 24.1 (C-23), 39.5 (C-24), 28.1 (C-25), 21.5 (C-26), 21.8 (C-27),
16.5 (C-28), 24.5 (C-29).
3b-Acetoxy-4a,14a-dimethyl-5a-cholest-8-en-7-one (6): mp ¼ 135–1368C
1
(hexane); yield: 34%. H NMR (500 MHz, CDCl3) d (ppm): 4.39 (H-3, ddd,
J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.68 (H-18, s), 1.02 (H-26, d,
J ¼ 2 Hz), 1.03 (H-27, d, J ¼ 2 Hz), 0.96 (H-21, d, J ¼ 6.4 Hz), 1.2 (H-19,
s), 0.73 (H-28, s), 0.86 (H-29, d, J ¼ 6.7 Hz), 2.05 (COOCH3, s). 13C NMR
(125 MHz, CDCl3) d (ppm): 33.5 (C-1), 28.5 (C-2), 76.70 (C-3), 36.6 (C-4),

1296
N. Mazoir et al.
46.2 (C-5), 39.1 (C-6), 197.5 (C-7), 139.7 (C-8), 164.4 (C-9), 38.7 (C-10), 24.5
(C-11), 30.1 (C-12), 44.9 (C-13), 47.80 (C-14), 30.9 (C-15), 30.60 (C-16), 51.4
(C-17), 15.40 (C-18), 18.1 (C-19), 36.3 (C-20), 18.60 (C-21), 36.4 (C-22),
24.0 (C-23), 39.4 (C-24), 27.8 (C-25), 22.7 (C-26), 22.5 (C-27), 25.4 (C-28),
15.0 (C-29), 170.7 (COOCH3). Low resolution: MS (m/z): 470.2 (10%),
283.2 (100%), 411.2 (50%), 117.2 (20%). High resolution: 470.3425 (calc.
470.3464).
3b-Acetoxy-4a,14a-dimethyl-5a-cholest-8-ene-7,11-dione (7): mp ¼ 117–
1
1198C (hexane), yield: 63%. H NMR (500 MHz, CDCl3) d (ppm): 4.40 (H-
3, ddd, J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.75 (H-18, s), 0.79 (H-26, d,
J ¼ 2 Hz), 0.83 (H-27, d, J ¼ 2 Hz), 0.84 (H-21, d, J ¼ 6.2 Hz), 1.24 (H-19,
s), 1.14 (H-28, s), 0.88 (H-29, d, J ¼ 6.6 Hz), 2.04 (COOCH3, s).13C NMR
(125 MHz, CDCl3) d (ppm): 33.6 (C-1), 31.3 (C-2), 77.2 (C-3), 35.2 (C-4),
47.1 (C-5), 39.2 (C-6), 201.0 (C-7), 151.6 (C-8), 152.1 (C-9), 38.4 (C-10),
202.5 (C-11), 51.4 (C-12), 47.4 (C-13), 47.6 (C-14), 32.1 (C-15), 27.3
(C-16), 48.9 (C-17), 16.7 (C-18), 16.2 (C-19), 36.5 (C-20), 18.5 (C-21), 34.9
(C-22), 24.1 (C-23), 39.4 (C-24), 27.7 (C-25), 21.8 (C-26), 22.1 (C-27), 26.1
(C-28), 14.7 (C-29), 170.6 (COOCH3).
3b-Tosyloxy-4a,14a-dimethyl-5a-cholest-8-en-7-one (8): mp ¼ 123–1248C
(methanol), yield: 35%. 1H NMR (500 MHz, CDCl3) d (ppm): 4.00 (H-3, ddd,
J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.72 (H-18, s), 0.98 (H-19, s), 0.84 (H-26,
d, J ¼ 2.1 Hz), 0.85 (H-27, d, J ¼ 2.1 Hz), 0.86 (H-21, d, J ¼ 6.2 Hz), 1.12
(H-28, s), 0.88 (H-29, d, J ¼ 6.6 Hz), 7.72 (H-20, d, J ¼ 8.8 Hz), 7.25 (H-30,
d, J ¼ 8.8 Hz), 2.44 (H-50). 13C NMR (125 MHz, CDCl3) d (ppm): 33.4
(C-1), 26.3 (C-2), 86.6 (C-3), 34.3 (C-4), 48.1 (C-5), 39.2 (C-6), 197.5 (C-7),
140.2 (C-8), 164.2 (C-9), 38.3 (C-10), 22.7 (C-11), 28.3 (C-12), 47.1 (C-13),
47.5 (C-14), 32.3 (C-15), 25.4 (C-16), 49.4 (C-17), 17.5 (C-18), 16.4 (C-19),
36.0 (C-20), 18.5 (C-21), 34.3 (C-22), 25.4 (C-23), 39.7 (C-24), 28.3 (C-25),
21.5 (C-26), 22.5 (C-27), 18.4 (C-30), 144.9 (C-10), 134.7 (C-20), 130.1
(C-30), 128.0 (C-40), 21.50 (C-50). Low resolution: MS (m/z): 395.3 (100%),
410.3 (43%), 424.3 (32%), 229 (22%), 582.3 (6%). High resolution:
582.3773 (calc. 582.3742).
3b-Tosyloxy-4a,14a-dimethyl-5a-cholest-8-ene-7,11-dione (9): mp ¼ 124–
1258C (hexane), yield: 60%. 1H NMR (500 MHz, CDCl3) d (ppm): 4.06
(H-3, ddd, J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.88 (H-18, s), 1.12 (H-19,
s), 0.85 (H-26, d, J ¼ 2.2 Hz), 0.86 (H-27, d, J ¼ 2.2 Hz), 0.87 (H-21, d,
J ¼ 6.4 Hz), 1.16 (H-28, s), 0.90 (H-29, d, J ¼ 6.4 Hz), 7.79 (H-20, d,
J ¼ 8.2 Hz), 7.31 (H-30, d, J ¼ 8.2 Hz), 2.43 (H-50). 13C NMR (125 MHz,
CDCl3) d (ppm): 33.5 (C-1), 26.2 (C-2), 86.5 (C-3), 34.9 (C-4), 48.6 (C-5),
39.4 (C-6), 200.5 (C-7), 151.4 (C-8), 150.7 (C-9), 38.2 (C-10), 202.7
(C-11), 51.5 (C-12), 47.7 (C-13), 47.5 (C-14), 32.5 (C-15), 27.5 (C-16),
49.5 (C-17), 16.5 (C-18), 16.4 (C-19), 36.4 (C-20), 18.5 (C-21), 34.8
(C-22), 28.4 (C-23), 39.5 (C-24), 31.8 (C-25), 21.5 (C-26), 22.5 (C-27),

Triterpene Derivatives
1297
14.5 (C-30), 26.2 (C-32), 144.3 (C-10),134.5 (C-20), 129.8 (C-30), 127.5 (C-40),
21.4 (C-50).
3b-Tosyloxy-4a,14a-dimethyl-5a-ergost-8-en-24-one (11): mp ¼ 145–
1
1468C (hexane), yield: 75%. H NMR (500 MHz, CDCl3) d (ppm): 4.09
(H-3, ddd, J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.86 (H-18, s), 1.54 (H-19,
s), 0.77 (H-21, d, J ¼ 6.37 Hz), 1.08 (H-26, d, J ¼ 1.52 Hz), 1.09 (H-27, d,
J ¼ 1.53 Hz), 0.93 (H-28, s), 0.88 (H-29, d, J ¼ 6.38 Hz), 7.79 (H-20, d,
J ¼ 8.31 Hz), 7.31 (H-30, d, J ¼ 7.9 Hz), 2.43 (H-50).13C NMR (125 MHz,
CDCl3) d (ppm): 33.5 (C-1), 26.2 (C-2), 88.8 (C-3), 44.5 (C-4), 49.2 (C-5),
22.7 (C-6), 22.0 (C-7), 133.4 (C-8), 135.2 (C-9), 38.2 (C-10), 20.7 (C-11),
51.5 (C-12), 47.7 (C-13), 47.5 (C-14), 32.5 (C-15), 27.5 (C-16), 49.5
(C-17), 16.5 (C-18), 16.4 (C-19), 36.4 (C-20), 18.5 (C-21), 34.8 (C-22),
28.4 (C-23), 215.5 (C-24), 31.8 (C-25), 21.5 (C-26), 22.5 (C-27), 144.6
(C-10), 135.3 (C-20), 129.9 (C-30), 128.5 (C-40), 21.5 (C-50). Low resolution:
MS (m/z): 582.3 (3%), 393.3 (42%), 395.3 (65%), 396 (25%), 407.3
(26%), 408.3 (27%), 409.3 (63%), 410.3 (70%), 424.3 (62%), 425.3 (25%),
442.3 (23%), 321.2 (22%), 343.2 (25%), 215.1 (25%), 241.2 (24%). High
resolution: 582.3758 (calc. 582.3742).
3b-Tosyloxy-4a,14a-dimethyl-5a-ergost-8-ene-7,24-dione (12): mp ¼ 152–
1538C (hexane), yield: 30%. 1H NMR (500 MHz, CDCl3) d (ppm): 4.10 (H-3,
ddd, J1 ¼ 11 Hz, J2 ¼ 11 Hz, J33 ¼ 3 Hz), 0.90 (H-18, s), 1.54 (H-19, s), 0.76
(H-21, d, J ¼ 6.40 Hz), 1.06 (H-26, d, J ¼ 2.00 Hz), 1.08 (H-27, d,
J ¼ 2.00 Hz), 0.95 (H-28, s), 0.88 (H-29, d, J ¼ 6.40 Hz), 7.77 (H-20, d,
J ¼ 8.40 Hz), 7.31 (H-30, d, J ¼ 8.00 Hz), 2.42 (H3-50).13C NMR (125 MHz,
CDCl3) d (ppm): 33.5 (C-1), 26.2 (C-2), 88.8 (C-3), 44.5 (C-4), 49.2 (C-5),
22.7 (C-6), 198.5 (C-7), 140.2 (C-8), 164.2 (C-9), 38.2 (C-10), 20.7 (C-11),
51.4 (C-12), 47.7 (C-13), 47.5 (C-14), 32.5 (C-15), 27.4 (C-16), 49.5 (C-17),
16.4 (C-18), 16.4 (C-19), 36.4 (C-20), 18.5 (C-21), 34.8 (C-22), 28.4 (C-23),
215.4 (C-24), 31.8 (C-25), 21.5 (C-26), 22.5 (C-27), 144.6 (C-10), 135.3
(C-20), 129.9 (C-30), 128.4 (C-40), 21.4 (C-50). Low resolution: 43.1 (22%),
91.1 (22%), 229.1 (24%), 302.2 (22%), 395 (26%), 424.3 (100%), 425.3
(31%), 596 (30%). High resolution: 596.3519 (calc. 596.3535).
3b-Tosyloxy-4a,14a-dimethyl-5a-ergost-8-ene-7,11,24-trione (13):
1
mp ¼ 155–1568C (methanol), yield: 64%. H NMR (500 MHz, CDCl3) d
(ppm): 4.10 (H-3, ddd, J1 ¼ 11 Hz, J2 ¼ 11 Hz, J3 ¼ 3 Hz), 0.91 (H-18, s),
1.45 (H-19, s), 0.80 (H-21, d, J ¼ 6.40 Hz), 1.06 (H-26, d, J ¼ 2.00 Hz),
1.08 (H-27, d, J ¼ 2.00 Hz), 0.95 (H-28, s), 0.88 (H-29, d, J ¼ 6.45 Hz),
7.78 (H-20, d, J ¼ 8.10 Hz), 7.33 (H-30, d, J ¼ 8.10 Hz), 2.43 (H-50). 13C
NMR (125 MHz, CDCl3) d (ppm): 33.2 (C-1), 26.1 (C-2), 86.4 (C-3), 35.8
(C-4), 47.3 (C-5), 38.3 (C-6), 200.7 (C-7), 151.4 (C-8), 150.9 (C-9), 40.9
(C-10), 202 (C-11), 51.50 (C-12), 49.1 (C-13), 47.5 (C-14), 32.1 (C-15),
27.3 (C-16), 49.2 (C-17), 16.9 (C-18), 16.4 (C-19), 35.8 (C-20), 18.4
(C-21), 38.2 (C-22), 29.8 (C-23), 214.5 (C-24), 35.6 (C-25), 21.7 (C-26),

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N. Mazoir et al.
22.4 (C-27), 31.8 (C-25), 21.5 (C-26), 18.4 (C-27), 14.5 (C-28), 16.4 (C-29),
144.7 (C-10), 134.6 (C-20), 129.8 (C-30), 127.8 (C-40), 18.4 (C-50). Low
resolution: 610.3 (2%), 395.3 (20%), 410.3 (21%), 423.3 (23%), 438.3
(100%), 439.3 (58%), 257.1 (20%), 229 (25%). High resolution: 610.3312
(calc. 610.3328).
ACKNOWLEDGMENTS
This work was partially supported by the Collaborative Project CSIC–
Laboratory of Natural Substances, University Cadi Ayyad, Faculty of Sciences
Semlalia Marrakesh (FSSM), Marrakesh, Morocco, Ref. 2004 MA 0009.
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